In Situ Structural Determination of a Homogeneous Ruthenium Racemization Catalyst and Its Activated Intermediates Using X-Ray Absorption Spectroscopy.
Karl P J GustafsonArnar GuðmundssonÉva G BajnócziNing YuanXiaodong ZouIngmar PerssonJan E BäckvallPublished in: Chemistry (Weinheim an der Bergstrasse, Germany) (2020)
The activation process of a known Ru-catalyst, dicarbonyl(pentaphenylcyclopentadienyl)ruthenium chloride, has been studied in detail using time resolved in situ X-ray absorption spectroscopy. The data provide bond lengths of the species involved in the process as well as information about bond formation and bond breaking. On addition of potassium tert-butoxide, the catalyst is activated and an alkoxide complex is formed. The catalyst activation proceeds via a key acyl intermediate, which gives rise to a complete structural change in the coordination environment around the Ru atom. The rate of activation for the different catalysts was found to be highly dependent on the electronic properties of the cyclopentadienyl ligand. During catalytic racemization of 1-phenylethanol a fast-dynamic equilibrium was observed.
Keyphrases
- highly efficient
- room temperature
- high resolution
- ionic liquid
- metal organic framework
- reduced graphene oxide
- carbon dioxide
- visible light
- molecular dynamics
- solid state
- transition metal
- gold nanoparticles
- electronic health record
- machine learning
- computed tomography
- magnetic resonance
- molecular dynamics simulations
- social media
- mass spectrometry
- deep learning
- solid phase extraction
- liquid chromatography
- contrast enhanced
- quantum dots